Manufacture of alkali metal silicates



July 4, 1944 R. F. RUTHRUFF 2,352,738

, MANUFACTURE OF ALKALI METAL SILICATES Filed Jan. l5, 1940 @Yew/vf ,y/J 55PM/97m Patented July 4, 1944 UNITED MANUFACTURE or ALKALI METAL sinron'rnsv Robert F. autumn, chicago, nl.

Application January 15, 1940, Serial No. 313,900

` claims. (Cl. zza-110) This invention vrelates to the manufacture of alkali metal silicates and means therefor. More particularly, this invention relates to'the method and means for the manufacture of alkali metal silicates wherein mixtures comprising siliceous material and an alkali metal compound are suspended in a moving stream of heated gas under the conditions necessary andAfor a period sufficient for interaction to occur with the formation of alkali metal silicates. More specifically, this invention relates to the manufacture of sodium silicates and means therefor. Stillmore specifically, this invention relates to the method and means for the manufacture of sodium silicates wherein mixtures comprising siliceous material and a sodium compound are suspended in a moving stream of Iheated gas under the conditions necessary and for a period sufficient. for interaction to occur with'the formation of cates.

The many uses of the alkali metal silicates, solutions of which in water are commonly referred to as water glass, are too familiar to require exposition. These alkali metal silicates may be formed in a variety of ways, but only two methods of preparation have achieved lastgng commercial success, these being (a) the fusion of a mixture of alkali metal carbonate and a suitable siliceous material at elevated temperatures, for example, 2400 to 2'100 F.. and (b) the fusion of a mixture of alkali metal sulfate, a 'suitable sill-- ceous material and a reducing agent, usually carbon, at elevated temperatures, for example. 2000 to 2'7001 F. In commercial practice, the alkali metal oxide-silica ratios of the product range from s ay 1:1 to 1:4.2 (mole basis), although somewhat wider variations are possible should sodium sili- `there be'any demand for products outside the range quoted. One of the most common varieties of alkali metal silicates is a sodium silicate having a sodium oxide-silica ratio of 1:3.4 (mole basis) or 1:3.22 (weight basis). To manufacture this material by the Yprocesses outlined, the following theoretical equations may be written:

furnaces, -but reverberatory furnaces may be used. Clay refractories are usually employed.

The attack of the refractories by the fusion mixture is very severe, this being' especially true in In both reactions, due to the large amount of silica in the fusion mixture, basic refractories are rapidly destroyed while the silica-alkali metal oxide equilibrium is such that siliceous refractories fail with almost equal rapidity. To overcome these difficulties, in some installations, the refractories are cooled. While this cuts down refractoryvdestruction. to a considerable extent, it is vobvious that this is accomplished only through an appreciable sacrifice in overall heat economy.

The alkali metal silicates prepared by the methods described above are obtained in the form of large glassy lumps. Before use these are usually dissolved in water to form the water glasses of commerce.4 The dissolving step is quite troublesome. If an attempt is made to dissolve these lumps in water, the sodium oxide is preferentially removed from the solid. which as a result becomes coated with an impervious layer of hydrated silica, which prevents or hinders further solution. The solid alkali metal silicate dissolves rather rapidly in an aqueous solution of alkali metal silicate, but here extreme care must be taken or the solution and solid will unite and fill the dissolving vessel with a tough solid that is almost impossible to remove. Usually, in dissolving solid alkali metal silicates, a solution of alkali metal silicates is used. A portion of the solutionis withdrawn continuously or from time to'tlme while van equivalent amount of water is added to the dissolving vessel. In this way solution occurs in a liquid medium sufficiently concentrated in solute to prevent hydrolysis of the solute but insuiciently concentrated in solute to enable the solution and solid to combine to form a solid mass in the dissolving vessel.

One object of this invention is to provide an improved process and means for the preparation of alkali metal silicates.

the preparation of alkali metal silicates and a suitable apparatus therefor. Another object of this invention is to provide a process and means for the production of alkali metal silicates wherein destruction of lfurnace refractories is at a minimum. An additional object of this inven- Briefly stated, in the\present invention, mixthe alkali metal sulfate-silica-carbon process. 55 tures 0f materials capable 0I, interatins at elef- A further object of thisl invention is to provide a continuous process for' f to the atmosphere.

vated temperatures, either of themselves of in the presence of a reducing agent, with the formation of alkali metal silicates are suspended in a moving stream of heated gas for a period suillcient for such .interaction to occur. For exam- ,ple, aggregates comprising an intimate mixture heated gas and after the desired reaction hasA occurred the resulting particles of alkali metal silicate may be separated from the gas streamby known means. ducing action may be furnished by the heate gas stream if desired.

In this last modification the re-.

Or, aggregates com- For a better understanding ofthe instant invention reference may be hadto the single figure, winch is a diagrammatic representation, partly in section and partly in elevation, of a suitable ap-"" paratus for carrying out the process of this invention. In Figure 1. numeral I designates a reactor suitable for the purposes of this invention. It

will be observed that this reactor takes the form of an elongated conduit having a sinuous conformation. The exact form and conformation of the reactor are largely matters of choice; in the present instance the particular conformation selected was chosen for the purpose of keeping the height of the reactor within reasonable limits. In the particular embodiment pictured, the reactor I is supplied with hot gases from hot gas producer 2, which are introduced into-the reactor i through line 3. Hot gas producer 2 is so constructed as to enable combustion to proceed therein at moderately elevated pressures, for example,

"pressures in the neighborhood of 45 pounds per square inch if desirable or necessary.

- Solid reactants are held in hopper or bin 4, which is most conveniently divided into an upper portion 5 and a lower portion 6, so arranged that when communication between 5 and 6 is closed 5 is open to the atmosphere, and when 5 and 6 are in communication 5 is clcsed to the atmosphere. This may be accomplished, for evample, by means of valves 1 and 8 mounted on valve stem 9. When these valves are lowered (as shown in Figure 1) communication between 5 and 6 is established but 5 is closed to the atmosphere. When valves 1 and 8 are raised, communication between 5 and 6 is cut off while 5 is. open By such means with the valves in the raised position it is possible to ll 5 with solid reactants without danger'of a blow back of gases from reactor I to the atmosphere. With the valves in the lowered position (shown in Figure 1), solid reactants in 5 may pass to 6, again without danger of blow back. Preferably, means are provided for heating the solid reactants in bin of hopper 4. In Figure 1, this heating means takes the form of a tubular heat exchanger in 6. Solid reactants flow through the` tubes I0 in this exchanger while the tubes themselves are surrounded by suitable heated uid entering through line II and leaving through actor I. By using a properly designed screw cohveyor, it is not absolutely essential to-divide bin or hopper 4 into upper and lower sections 5 and -separated by valve 8. Properly designed screw conveyors are able to seal against appreciable pressure so that I3 acts to prevent blow backs from reactor I through hopper 4. However, as a safety precaution, it ,is'well to design hopper or bin 4 as described or in a similar fashion. If desired, solid reactants may be discharged. by

Vscrew I3 into a Venturi throat I4 disposed in reactor I. By this means suspension of the solid reactants in the gases entering through 3 is greatly facilitated.

The suspension of solid reactants in the gases entering-through line 3 passes through reactor I in which reaction occurs. The reaction prod-5 ucts leaving reactor I are in a highly heated condition and should be cooled appreciably-before being worked up. This may be accomplished by any suitable means, for example by spraying water into the'suspension through line I5 or by passing the suspension over coils I6 through which water is flowing or both.

Reaction products are now separated from the partially cooled suspension. This separation is usually accomplished in two steps. A rough separation occurs in the first, while the greaterl part of the remaining reaction products is removed in the second. Any suitable separation means may be employed. In Figure l theuse of a gravity separator and a cyclone-separator in series is shown, but other separation means, for example Cottrell precipitators, may be used. In Figure 1, the partially cooled suspension is shown passing to gravity separator- I1 through line I8. In gravity separator I1, the velocity of the suspension is much reduced and the direction of flow is changed several times. Separated solids may be removed through lines I9. Partially separated suspension is sent from gravity separator I1 through line 20 to cyclone separator 2I, where practically complete removal of solid reaction products occurs, these being removed through line 22..

The practically solidfree-gas leaves cyclone separator- 2i through line 23 and passes to air preheater 24, leaving through line 25. Part ofthe stream in line 23 may be diverted through line II to preheat solid reactants as previously described. Air enters air preheater 24 through sired or necessary, a suitable amount of gaseous.'

liquid or solid fuel may be introduced into the preheated air stream via line 28, this fuel then being partially or completely burned in hot gas producer 2.

As the suspension leaving reactor I contains appreciable sensible heat, it is advisable to recover as much of this as possible in the form of useful work. This may be done in a number oi ways. For example, large amounts of steam may be generated in coil I6. Also, the hot gas may be usedto drive a turbine, although it is preferably used for this purpose only after the solids suspended therein have been removed. As shown in Figure 1,'part of the heat content of the gas is recovered and used to preheat air While another part is devoted to preheating the solid reactants.

As temperature conditions are very severe in While the reactor shown in Figure 1 consists of an elongated conduit of sinuous form having three legs in which the reactants first pass upward. then downward and then upward again. this -particular conformation is illustrative only and in no way limits the scope `of the invention. The number of legs possessed by the reactor and the direction of flow therein are immaterial. For example, instead of the reactor shown, equally satisfactory results are obtained with reactors having one, two, four or more legs. Also, it is not necessary to introduce the reactants into an ascending leg of the reactor. Reactants, if desired, may .be introduced into the upper portion of a descending leg and such reactors may again have one ormore legs. Also, while in F gure 1 the reactor is shown disposed vertically, equally satisfactory vresults have been obtained using horizontal reactors or reactors with alternating Vertical and horizontal legs.

Figure 1 and the above description relating thereto cover one embodiment of an apparatus suitable for the present invention. Further details, including quantities, temperatures, rates and the like, as well as a few of the `many possible modifications of the apparatus shown and described will be outlined in the ve examples to follow.

Example 1 Finely divided siliceous material, for example, diatomaceous earthflour, is made into a thick but uniform paste with a strong solution of sodium carbonate. For each 100 pounds of siliceous material used about 52 pounds of sodium carbonate are employed. The paste is evaporated to dryness, is crushed and charged to hopper or bin 4 of a semi-commercial unit similar to that shown in Figure 1. A natural gas comprising essentially methane is charged to the hot gas producer 2 through line 28 at a rate of about 16 cubic feet per minute. In this modification of the general method for producing alkali metal silicates, the hot gas stream may be inert, oxidizing or reducing in its action. For heat economy an inert hot gas stream is used; that is, the theoretical amount of air is added to hot gas producer 2 through line 21. The hydrocarbon gas is burned in a suitable burner. Circulation is continued without the introduction of solid reactants until the whole system is brought up to temperature, at which time screw I3 is started and the mixture of siliceous material and sodium carbonate is introduced into the reactor at a rate of about 13.5 pounds per minute. Conditions are so regulated that the temperature in cyclone separator 2i is somewhat above 1000 F., while the temperature of the air in line 21 and the solid introduced into reactor I is somewhat above 850 F. As farl as can be measured, the temperature in reactor l varies between 2400" F. and 2700" F., but little reliance cany be placed on these determinations. Finely divided sodium silicates `are vremoved through lines I9 and 22 at total rate u Example 2 One hundred parts by weight of finely divided siliceous matter, for example diatomaceous earth flour, is made into a thick but uniform paste with a strong solution containing '70 parts by weight of sodium sulfate. The resulting paste is dried. and is crushed and mixed with about 24 parts by weight of the petroleum fraction representing 20% bottoms from Mid-Continent crude and hav-' ing an A. P. I. gravity of 17.6. The resulting mixture is heated in an inert atmosphere to drive off all -volatile matter and the dry product is crushed and charged into hopper or bin' d of an apparatus similar to that shown in Figure 1. A natural gas comprising essentially methane is charged at a rate of 8 cubic feet per minute, through line 28,I to the hot gas producer 2. In this modification of the general method forproducing alkali metal silicatesthe hot gas stream may be inert or reducing in its action. For heat economy it is advisable to operate using the theoretical amount of air providing that combustion is perfect; otherwise a slight deciency of air should be used to insure that the hot combustion gases contain no oxygen. Air is added to hot gas producer 2 through line 21 to burn the methane. Hot gas circulation is continued without introduction of solid reactants until the whole system is brought up to reaction temperature, at' which time screw I3 is started and the siliceous material-sodium sulfate-carbon mixture is introduced into the reactor at a rate oi' about 5 pounds perminute. Temperatures are similar to those described in Example 1. Product is removed from lines I9 and line 22 at a total rate of a little above 3.5 pounds per minute.

Example 3- In this example, as the hotQ gas isproduced autogenously, hot gas producer 2 is not required except perhaps initially when it is preferably used to bring the whole apparatus up to temperature. If desired, a bypass between line 21 and line 3 may be constructed so as to short circuit hot gas producer 2 when temperature has been achieved. A mixture of siliceous material and soda ash is prepared as described in Example 1 and, after drying, petroleum coke is added at a rate of 8 pounds per 100 pounds of siliceous material-sodium carbonate mixturethe whole then being mixed andpulverized and added to hopper or bin of an apparatus similar to that shown in Figure 1. The whole apparatus is brought up to temperature by burning fuel in hot gas producer 2, following which this is gradually discontinued, solid reactants being simultaneously cut into reactor I by starting screw i3 while preheated air is added to line 3 from line 21, either directly by a bypass (not shown) or via hot gas producer 2. Under settled conditions solid reactants are added to reactor I at a rate of about 15.5 pounds per minute while preheated air is added to line 3 at a rate of 185 cubic feet per minute, measured at standard conditions. Temperatures are similar to those desrid in Example 1. Alkali met-al silicates are removed from lines I9 and` line22 at a total rate of about 12.5 pounds per minute.

Example 4 Again in this example the hot gas is produced autogenously, so that hot gas producer 2 of Figure l is not required except perhaps initially when it is preferably usedto bring the whole apparatus up to temperature. If desired, a bypass between line 21 and line 3 may be used to short circuit hot gas producer 2`when temperature has been achieved. A mixture of siliceous material and sodium sulfate is prepared in the proportions specified in'Example 2. To 100 parts byweight of the dried .mixture are added 12 pounds of carbon, for example petroleum coke. The whole is pulverized and charged to hopper or bin 4 of an apparatus similar to that shown in Figure 1. The whole apparatus is brought up to temperature by burning fuel in hot lgas lproducer 2, following which thisjis gradually discontinued, solid reactants being simultaneously cut into reactor I by starting screw i3 while preheated air is added to line 3 4from line 21 either directlyv by a bypass (not shown) o'r via hot gas producer 2. vUnder settled conditions, solid reactants are added to reactor l at a rate of about 6.35 pounds per minute while preheated air is added to line 3 at a rate of about 100 cubic feetvper minute, measured at standard conditions. Temperatures are similar to those described in Example 1. Alkakli metal silicates are removed from lines I9 and line 22 at a total rate of about 4.35 pounds per minute. Example A mixture of siliceous material and sodium sulfate isvprepared in the proportions specied in Example 2, the dried and pulverized mixture be-4 ing placed in bin or hopper 4 of an apparatus similar to that shown in Figure l. Producer gas containing 25% carbonmonoxide and half as much hydrogen is passed to hot gas producer 2 bymeans of line 28 at a rate of 58 cubic feet 5v a used. Preferably such material should have a per minute, measured at standard conditions.

This producer gas is at a temperature of somewhat -above 850 F. and preferably has a low content of solids. Air is introducedinto the hot gas producer through line 21 at a rate of 38 cubic feet per minute. measured at standard condivtures are approximately as specified in Example 1.

To summarize and recapitulate, ve modifications of the general method for the preparation of alkali metal silicates have been brieily described in the foregoing examples. These modifications may conveniently be divided into two general classes: (a) wherein the siliceous material is mixed with an alkali metal compound capable of reacting directly with siliceous material, with the formation of alkali metal silicates, as exemplified by Examples 1 and 3, and (b) wherein the siliceous material is mixed with an alkali metal compound that ilrst must be reduced prior to reacting with the siliceous materialwith the formation of alkali metal silicates. as exemplied by`Examples 2, 4, and 5. In Example l, a mixture of siliceous materialand sodium carbonate is suspended in a stream of highly heated gas for atime sufilcient for the formation. of sodium silicate to occur. In Example 3, a similar mixture is incorporated with combustible matter and the whole is suspended in a moving stream of oxidizing gas. The oxidation of the combustible matter heats the whole to reaction temperature and sodium silicates form. In Example 2, a mixture oi' siliceous material, sodium sulfate and csrbon is suspended in a moving stream of highly heated inert gas. Under the existing temperature conditions the sodium sulfate is reduced to the oxide, which in turn reacts with the siliceous material to form sodium silicates. Example 4 is similar except that an oxidizing gas is employed together with suilicient carbon to both raise the whole to reaction temperature and re.-

duce sodium sulfate to the oxide. In Example 5, a mixture of siliceous material and sodium sulfate is suspended in a movingtream oi.' Sas having reducing properties, which converts sodiumrsulfatetothe oxide. l While the instant invention has been elucidated by means of a showing and a description of an apparatus suitable for. the accomplishment of the objects thereof and by the recital of numerous examples of various modificationsthereof, it is to be understood that this apparatus and these examples are illustrative only and are included for the purpose of familiarizing those skilled in the art to which the instant invention pertains with the general scope thereof. Many modifications of the instant invention will readily occur to those skilled in the art to which it pertains.

While the use of carbonaceous material commonly known as petroleum coke or oil coke is described in Examples 2, 3 and 4, it is obvious that other suitable carbonaceous material may be low ash content. Other suitable materials for the formation of carbonaceous matter ln accord with the teachings of Examples 2 and 4 include molasses and coal tar pitches. Also, part or all of the carbonaceous matter may be added to the, solid reactants in other forms and in other ways4 than as described in these two examples. For instance, in Example 3, instead of proceeding as described, a silica-sodium carbonate mixture may black, low ash coal, or the likev per 100 pounds of mixture, and the whole charged to hopper or4 bin 4. Similarly, in Example 4, a silica-sodium sulfate-carbon mixture may be made using the proportions of Example 2, and to this` may be added about 10 parts by weight of petroleum coke, carbon black, low .ash coal, or the like per 100 parts of the silica-sodium carbonate-carbon, and I terial'eapable of. reacting directly with siliceous material to form sodium silicates, .many equivalents, such as sodium oxide, sodium peroxide, and sodium hydroxide, and 'salts capable of forming one of these when thermally decomposed, may be substituted therefor. i Likewise .equivalents for the sodium sulfate mentioned in some example! as illustrative of a compoundlthat must be reduced prior to reaction with siliceousmaterial will occur to those skilled in the art.

While in the examples sodium compounds have been cited exclusively, other alkali metal compounds may be substituted. While at present no uses requiring lithium, caesium or rubidiurn silicates are known, in a few minor applications the use of potassium silicates is almost essential, for example as binders in the manufacture of carbon arc electrodes when it is desired to eliminate the strong sodium lines. Also, since potassium silicates eiioresce to a lesser extent than sodium silicates of corresponding composition, the former are commonly employed in silicate paints.

In the examples the siliceous material and sodium salt are so proportioned as to give silicates having a sodium oxide-silica ratio of 113.4, calculated on the mole basis. While this ratio is a very common one in commercial silicates, obviously the instant invention is not limited to the production of silicates of this ratio, this constant ratio being employed in the examples simply to facilitate comparisons between the various processes.

The manifold advantages of the instant invention'are obvious. In the rst place, the process is continuous and a simple apparatus is employed. The desired product is obtained in the form of ne solidified globules, which are brought into solution with extreme ease, especially after being pretreated in an atmosphere of steam.`ll Furthermore. the life of the refractories employed -is extremely long, due to the conducting of the reaction in the suspended phase, which reduces contact between reactants and reiraotories to a minimum. The long refractory life results in a twofold advantage. In the rst place, furnace repairs and accordingly apparatus shut-downs are at a minimum and, secondly, contamination of the final product With materials from the refractories is at a minimum. This 'results in a nal product that dissolves easily and completely to form a clear solution.

I claim:

1. In the manufacture of alkali metal silicates, the steps including, suspending particles comprising aggregates of an alkali metal compound and a siliceous material in a moving stream of heated gas wherein said particles are subjected to reaction conditions to effect the formation of molten particles of alkali metal silicates, cooling the resulting suspension to solidify said particles of alkali metal silicates and separating said solidified particles of alkali metal silicates from said gas stream.

2. In the manufacture of sodium silicates, the steps including, suspending particles comprising aggregates of sodium carbonate and siliceous material in a moving stream of heated gaswherein said particles are subjected to reaction conditions to effect the formation of molten par., ticles of sodium silicates, cooling the resulting suspension. to solidify said particles of sodium silicates and separating saidsolidied particles of sodium silicates from said gas stream.

3. In the manufacture of sodium silicates, the

steps including, suspending particles comprising aggregates of sodium sulfate and a siliceous material in a moving stream of heated gas wherein said particles are subjected to reaction conditions to effect the formation of molten particles of sodium silicates, cooling the resulting suspension to solidfy said particles of sodium silicates and separating said particles of sodium silicates from said gas stream.

4. The process of claim 2, wherein'said moving stream of gas is brought to reaction temperature by the combustion of carbonaceous matcrialrintimately mixed with said aggregates comprising sodium carbonate and a siliceous material.

v5. The process of claim 3, wherein said moving stream of gas is brought to reaction temperature by the combustion of carbonaceous material intimately mixed With said aggregates comprising sodium sulfate and a' siliceous material.

ROBERT F. RU'I'HRUFF. 

